Beryllocene
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3D model (JSmol)
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PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |
| C10H10Be | |
| Molar mass | 139.202 g·mol−1 |
| Appearance | colorless crystals |
| Melting point | 59 °C (138 °F; 332 K) |
| Boiling point | 233 °C (451 °F; 506 K) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Beryllocene is an organoberyllium compound with the chemical formula Be(C5H5)2. It was first prepared in 1959.[1] The colorless substance can be crystallized from petroleum ether in the form of white needles at −60 °C and decomposes quickly upon contact with atmospheric oxygen and water.[2]
Preparation
[edit]Beryllocene can be prepared by reacting beryllium chloride and sodium cyclopentadienide in benzene or diethyl ether:[2]
![{\displaystyle \mathrm {BeCl_{2}+\ 2\ Na(C_{5}H_{5})\ {\xrightarrow[{}]{Et_{2}O}}Be(C_{5}H_{5})_{2}+2\ NaCl} }](https://wikimedia.org/api/rest_v1/media/math/render/svg/33e08a4ccd04cd296a33378ea95ba151f63644a2)
Properties
[edit]Physical
[edit]In contrast to the uncharged metallocenes of the transition metals V, Cr, Fe, Co, Ni, Ru and Os, which have a strictly symmetrical and therefore dipoleless structure, beryllocene has a electric dipole moment of 2.46 Debye (in benzene), or 2.24 Debye (in cyclohexane), indicating asymmetry of the molecule. In the IR spectrum there are signals at 1524, 1610, 1669, 1715 and 1733 cm−1, which also indicate that the structure does correspond to that of ferrocene.[2] In contrast, the nuclear magnetic resonance spectrum shows only one signal down to −135 °C, indicating either a symmetrical structure or a rapid fluctuation of the rings.[3]
Structure
[edit]Beryllocene shows different molecular geometries depending on the physical state. The low-temperature X-ray structure analysis shows a slipped sandwich structure, i.e. the rings are offset from each other - one ring is η5 coordinated with a Be-Cp distance of 152 pm, the second only η1 coordinated (Be-Cp distance: 181 pm).[4][5][6] The reason for the η5, η1 structure is that the orbitals of beryllocene can only be occupied with a maximum of 8 valence electrons. In the gas phase both rings η5 appear to be coordinated. In fact, one ring is significantly further from the central atom than the other (190 and 147 pm) and the apparent η5 coordination is due to a rapid fluctuation of the bond.[7] Based on gas-phase electron diffraction studies at 120 °C, Arne Haaland concluded in 1979 that the two rings are only about 80 pm shifted from each other and are not coordinated η5,η1, but rather η5,η3.[3]
Like beryllocene, the octamethyl derivative Be(C5Me4H)2 has a slipped sandwich structure with η5,η1 coordination. In contrast Be(C5Me5)2 shows the classic η5,η5 coordination. In the crystal, however, the Be-C distances vary between 196.9(1) and 211.4(1) pm.[8]
Chemical
[edit]Beryllocene decomposes relatively quickly in tetrahydrofuran, forming a yellowish gel. It reacts violently in water to produce beryllium hydroxide and cyclopentadiene:[2]
- Be(C5H5)2 + 2 H2O → Be(OH)2 + 2 C5H6
Like magnesocene, beryllocene also forms ferrocene with iron(II) chloride.[2] The driving force is the formation of the very stable ferrocene molecule.
- Be(C5H5)2 + FeCl2 → BeCl2 + Fe(C5H5)2
It is predicted to react with beryllium to generate C5H5BeBeC5H5.[9]
Safety
[edit]Beryllocene is toxic and carcinogenic.
References
[edit]- ^ Rafael Fernández, Ernesto Carmona (Aug 2005). "Recent Developments in the Chemistry of Beryllocenes". European Journal of Inorganic Chemistry. 2005 (16): 3197–3206. doi:10.1002/ejic.200500329. ISSN 1434-1948. Retrieved 2020-09-29.
- ^ a b c d e Fischer, Ernst Otto; Hofmann, Hermann P. (Feb 1959). "Über Aromatenkomplexe von Metallen, XXV. Di‐cyclopentadienyl‐beryllium". Chemische Berichte. 92 (2): 482–486. doi:10.1002/cber.19590920233. ISSN 0009-2940.
- ^ a b Almenningen, Arne; Haaland, Arne; Lusztyk, Janusz (May 1979). "The molecular structure of beryllocene, (C5H5)2Be. A reinvestigation by gas phase electron diffraction". Journal of Organometallic Chemistry. 170 (3): 271–284. doi:10.1016/S0022-328X(00)92065-5.
- ^ Elschenbroich, Christoph (2008). Organometallchemie. Teubner Studienbücher Chemie (6., überarb. Aufl ed.). Wiesbaden: Teubner. ISBN 978-3-8351-0167-8.
- ^ Wong, C. H.; Lee, T. Y.; Chao, K. J.; Lee, S. (1972-06-15). "Crystal structure of bis(cyclopentadienyl)beryllium at –120°C". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 28 (6): 1662–1665. doi:10.1107/S0567740872004820.
- ^ Huheey, James E.; Keiter, Ellen A.; Keiter, Richard L.; Steudel, Ralf; Huheey, James E. (2003). Anorganische Chemie: Prinzipien von Struktur und Reaktivität (3., durchges. Aufl ed.). Berlin: de Gruyter. ISBN 978-3-11-017903-3.
- ^ Riedel, Erwin; Alsfasser, Ralf, eds. (2007). Moderne anorganische Chemie: mit CD-ROM (3. Aufl ed.). Berlin: de Gruyter. ISBN 978-3-11-019060-1.
- ^ del Mar Conejo, María; Fernández, Rafael; Gutiérrez-Puebla, Enrique; Monge, Ángeles; Ruiz, Caridad; Carmona, Ernesto (2000-06-02). "Synthesis and X-ray Structures of [Be(C5Me4H)2] and [Be(C5Me5)2]". Angewandte Chemie (in German). 112 (11): 2025–2027. doi:10.1002/1521-3757(20000602)112:11<2025::AID-ANGE2025>3.0.CO;2-A. ISSN 0044-8249.
- ^ Xie, Yaoming; Schaefer, Henry F.; Jemmis, Eluvathingal D. (2005). "Characteristics of novel sandwiched beryllium, magnesium, and calcium dimers: C5H5BeBeC5H5, C5H5MgMgC5H5, and C5H5CaCaC5H5". Chemical Physics Letters. 402 (4–6): 414–421. doi:10.1016/j.cplett.2004.11.106. ISSN 0009-2614.